Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 35, No. 2, p.

130-136 (February 1998)

Trivalent f-Element Intra-group Separation

by Solvent Extraction with CMPO-complexant System

Yoshikazu KOMAt, Masayuki WATANABE, Shinichi NEMOTO and Yasumasa TANAKA

Power Reactor and Nuclear Fuel Development Corporation*

(Received September 3, 1997)

For trivalent actinide and lanthanide separation, the solvent extraction system which employs neutral bifunc-
tional extractant n-octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and aminopoly-
acetic acid was investigated. The system is based on CMPO-tri-n-butylphosphate (TBP) mixed solvent and
diethylenetriaminepentaacetic acid (DTPA)-sodium nitrate solution. The separation is achieved by com-
plexing trivalent actinide preferentially with DTPA in aqueous phase and extracting lanthanide into organic
phase. Mutual separation between light lanthanide, Am and Cm was mainly governed by complex formation
with DTPA. The acidity is most affecting parameter for partitioning and its increase results in decrease of
distribution ratio. For selective stripping of trivalent actinide from 0.2M CMPO-1.0M TBP in n-dodecane at
room temperature, 0.05M DTPA and 2-4M sodium nitrate solution (pH 2) is useful. From the observed dis-
tribution behavior, a basic flow sheet which is composed of four steps was proposed. In batchwise experiments
with radioactive nuclides, separation factor of larger than 13 and 27 for Ce/Am and Cm/Eu, respectively,
were obtained and the applicability of the system was indicated.

KEYWORDS: solvent extraction, separation process, americium, curium, lanthanides,

CMPO, DTPA, sodium nitrate, TBP, pH value

concentrated nitrate system for enhancement of extrac-

I. Introduction
The separation of trivalent 4f- and 5f-elements has
been a major concern for the chemists who engaged in
partitioning of high level liquid waste. Recovery pro-
cess for Am and Cm has been studied and developed
for some decades by many researchers(1)-(5).Amine and
acidic organo-phosphoric extractant are well-known ex-
tractants for this purpose. The TRAMEX process em-
ploys amine extractant with concentrated chloride so-
lution as aqueous phase(1). The extraction with amine
proceeds through anion exchange mechanism. The chlo-
ride media gives more selective extration than nitrate
media, but the environment for operation have to be
corrosive. On the other hand, the TALSPEAK process
uses acidic extractant, bis(2-ethylhexyl)phosphoric acid
(HDEHP) and an aminopolyacetic acid, diethylenetri-
aminepentaacetic acid (DTPA) as a selective stripping
reagent(2), and the extraction with HDEHP proceeds
through cation exchange mechanism. Therefore, the ex-
traction must be performed in low acidic medium, and
is very sensitive to the change of pH.
Studies on the separation of Am and Cm from lan-
thanides using neutral extractant have been reported
in limited quantity. A typical neutral extractant, tri-
n-butylphosphate (TBP), was also studied for this pur-
pose(4)(5). TBP is used with DTPA since TBP is less
selective and, in addition, TBP must be used in highly
*T
okai-mura, Naka-gun, Ibaraki-ken 319-1194.
Corresponding author, Tel. +81-29-282-1111,
t of Am and Cm is discussed.
Fax. +81-29-283-2164, E-mail: koma@tokai.pnc.go.jp
tion. It is widely considered that TBP is not suitable for
mutual separation of trivalent f-elements.
The n-octyl(pheny1)-N, N-diisobutylcarbamoylmethyl-
phosphine oxide, which is commonly referred as CMPO,
has been developed to extract Am and Cm from highly
acidic solution(6). The TRUEX process employs the
CMPO-TBP mixed solvent and has been proved useful
for the recovery of Am and Cm from various acidic solu-
tion(7)(8). The raffinate from co-decontamination cycle of
PUREX process is a typical acidic solution for treatment
with TRUEX solvent. The TRUEX process is a promis-
ing candidate to construct separation flow sheet that is
feasible for PUREX process without appreciable change
in the composition of feed aqueous solution. However, as
the TRUEX solvent is effective not only for trivalent ac-
tinide but also lanthanide, the recovered americium and
curium fraction contains trivalent lanthanide. In order
to remove lanthanide from americium and curium frac-
tion, the TRUEX process must be essentially modified
or additional chemical procedures have to be adopted to
the original TRUEX process.
As described above, the strong extracting ability of
CMPO should be pursued for the simplicity of the to-
tal chemical process for spent nuclear fuel reprocessing
and subsequent waste treatment. In the present paper,
we examine the application of CMPO-nitrate partition
system to the mutual separation of trivalent actinides
and lanthanides using DTPA as a selective complexing
reagent and, then, a process flow sheet for the recovery

130
Trivalent f-Element Intra-group Separation by Solvent Extraction 131

II. Experiemental III. Results and Discussion

1. Reagent 1. Reactions Related to Separation
CMPO was purchased from Atochem North America, Some of aminopolyacetic acids are known as selec-
Ltd. and diluted with TBP and n-dodecane to obtain a tive complexing reagents for trivalent actinide and lan-
TRUEX solvent of 0.2M CMPO-1.0M TBP-n-dodecane. thanide. The carboxylic groups in an aminopolyacetic
DTPA was supplied from Kanto Chemical Co., Inc. in acid have dissociative protons and the dissociated prod-
its sodium form (as a 40% solution). Sodium nitrate was uct has chelating ability with metallic cations. The acid
used as a salting-out reagent. dissociation of DTPA are expressed as;
For experiments with inactive elements (cold experi-
H5-nDTPAn_??_H++N4-nDTPA(n+1)-,
ments), nitrate of Ce, Nd, Eu and Dy were used as repre-
sentatives of lanthanides. A 1M sodium nitrate solution n=0-4. (1)
which contained 0.0025M of each lanthanide was pre-
Because the first and second pKa values are 1.80 and
pared and used to make a loaded TRUEX solvent. As a
stripping solution, 0.01-0.1M DTPA and 1-5M NaNO3 2.55, respectively(9), the acid dissociation of DTPA does
mixed solution was examined. The pH value of each not proceed in a highly acidic media like a concentrated
stripping solution was controlled by adding nitric acid. liquid waste from PUREX reprocessing plant. Thus,
For examining partition behaviors of Am and Cm DTPA have to be used in higher pH than unity. On
as well as radioactive lanthanides, a batchwise strip- the other hand, hydrolysis of heavy metallic cation must
be suppressed in partition system. Therefore, the pH
ping experiment (hot experiment) was performed by us-
ing a TRUEX product. The TRUEX product solu- must be lower than around 4.
tion which contained 6.3x107Bq/cm3 of 144Ce, 4.9x Extraction of trivalent metal cation with CMPO and
106Bq/cm3 of 154Eu, 1.6x107Bq/cm3 of 155Eu, 1.1x complexing with DTPA are represented by followingtwo
107Bq/cm3 of 241Am, 8.4x105Bq/cm3 of 242Cm and equations, respectively:
1.5x106Bq/cm3 of 244Cm, respectively, was supplied M3++3NO3-+3CMPO_??_M(NO3)3,3CMPO (2)
from TRUEX counter-current experiment which was car-
ried out in hot cells of the Chemical Processing Facility M3++DTPA5-_??_M,DTPA2-. (3)
(CPF) at Tokai Works, PNC. The above aqueous so-
lution was diluted 15 times with NaNO3 solution to be The stability constants of DTPA-Am and DTPA-Cm
a 0.1M HNO3-1.0M NaNO3 solution before the contact complexes are higher than DTPA-lanthanides corn-
with fresh TRUEX solvent. A 0.05M DTPA-4M NaNO3 plex(9)(10).Thus, DTPA preferentially forms complexes
solution (pH 2.0) was used as a stripping solution. with Am and Cm rather than coexisting lanthanides.
Although the extracting ability of CMPO was firstly
2. Procedure proved by using highly acidic solution, the extraction
The TRUEX solvent for cold experiments was shaken with CMPO is possible from lower acidic medium if ni-
in advance with 0.01M nitric acid solution, and contacted trate anion coexists in a sufficient concentration. For the
with the stock solution of lanthanides to make a loaded separation of Am and Cm from lanthanides, it is neces-
solvent. The loaded solvent was mixed with a stripping sary to find out the condition in which americium and
solution that had a controlled pH value between 1 and curium form complexes with DTPA in an aqueous phase
3. The contact was made in a thermostatted chamber while lanthanides are retained in the organic phase.
by using a vortex mixer. After centrifuging to separate In the partition system of TRUEX solvent and DTPA-
phases, the pH of the aqueous phase was measured by nitrate solution, many factors, such as pH, concentration
using a pH meter (HM-60V, Toa Electronics Ltd. or pH of nitrate ([NO3-])and concentration of DTPA ([DTPA])
82, Tokyo Garasu Kikai, KK). The concentration of each affect the distribution of trivalent actinides and lan-
lanthanide was determined by using ICP-AES (ICPS- thanides. In order to find out the optimum condition
2000, Shimadzu Corp.). of separation, it is necessary to know the dependence
The hot batchwise experiments was carried out in a on the distribution ratio (D) to these parameters. Ac-
hot cell of CPF. The 0.1M HNO3-1.0M NaNO3 solution cording to Moeller(9) and Baybarz(10), the stability con-
containing radioactive lanthanides, Am and Cm was con- stant of DTPA-Dy complex is the highest among those
tacted with TRUEX solvent for 5min to obtain a loaded of lanthanides and therefore the nearest to that of Am.
solvent. The loaded solvent was shaken with a strip- The distribution ratio of Dy with TRUEX solvent is a
ping solution for 30min. The contents of 149Ce, 159Eu little bit lower than that of Am(11). The differences be-
and 166Eu were determined by g-ray spectrometry, and tween Am and Dy in complex formation and extraction
those of 241Am, 242Cm and 244Cm was determined by will compensate to indicate similar behavior in TRUEX
-ray spectrometry. a solvent and DTPA-nitrate system. Therefore, we se-
lected Dy as a substitute of Am. A series of cold experi-
ments werecarried out to see the influenceof pH, [NO3-],
[DTPA],temperature and shaking time to D values.

VOL. 35, NO. 2, FEBRUARY 1998

 Y. KOMA et al.
132

2. Fundamental Property of the Partition

System
The dependence of D values on pH is shown in Fig. 1.
At pH values lower than 1.5, D values of these lan-
thanides are larger than 100 and almost identical. DTPA
does not dissociate and the complex formation with
DTPA does not occur in such an acidic solution.
The D values decreases with increasing pH. The de-
crease coincides with the appearance of significant differ-
ence in D values of lanthanides at pH higher than 1.8.
The D value decrease with increasing atomic number,
and it is the reverse order of the stability constant of
DTPA complex. Obviously, the complex formation with
DTPA reduces D value and makes the lanthanides mu-
tual separation possible. As it is considered that Am
behaves like Dy and the stability constant of DTPA-Cm
complex is larger than that of Am(10), we can expect
that the separation of light lanthanide, such as Ce and
Nd, and trivalent actinides can be achieved by stripping
the actinides with DTPA-nitrate solution. The slope
of log D vs. pH plots are nearly -3 for these four lan-
thanides at pH higher than 2.0. This means that the Fig. 2 Dependency of lanthanides distribution on sodium
separation factor which is defined by the ratio of D val- nitrate concentration

ues for adjacent lanthanides pair is almost constant when

pH is higher than 2. The condition of pH higher than 2 is
neither suitable nor necessary for the separation of triva- thanides, Ce and Nd, are large enough to retain them
lent actinides from light lanthanides, since the D values in organic solution, while Dy as the substitute of Am
should be kept large enough to retain light lanthanides is transported into the aqueous phase by complexing
in the organic phase. DTPA. Separation factors, calculated as the ratio of dis-
The dependence of D on [NaNO3] is shown in tribution ratio to that of Dy, are plotted against sodium
Fig. 2. As the concentration of nitrate increases, dis- nitrate concentration in Fig. 3. The separation factor
tribution ratio also increases. When the condition of is almost independent of nitrate concentration, and the
2M<[NaNO3[<4M is adopted, the D values of light lan- value is roughly equal to the ratio of stability constant
of DTPA complex. This suggests that the separation is
governed by the complexing with DTPA. The decrease of
D with increasing [DTPA] is shown in Fig. 4. The slope
is approximately -1, which corresponds to 1:1 complex
of DTPA and a lanthanide.
Fast kinetics is desired for practical separation process.
The dependency on shaking time is shown in Fig. 5.
After a few minutes of mixing, the distribution ratio
value became constant. The kinetics of stripping is quite
fast enough to use mixer-settler type contactor for a
counter-current operation.
As shown in Fig. 6, the distribution ratio decreases
with the increase in temperature. The extraction with
CMPO is known as exothermic(12) and the increase in
temperature will suppress the extraction. On the other
hand, the dissociation of DTPA is endothermic(9) and
complexing with DTPA is exothermic. As the result,
the effect of exothermic complex formation with DTPA
is apparently compensated, and the observed tendency
on temperature would mainly reflect the nature of the
extraction reaction with CMPO.
The acid transfer between two phases is not negligi-
ble and will disturb the partitioning system. The change
Fig. 1 Dependency of lanthanides distribution on pH at of pH through back-extraction process, referred as A.pH,
equilibrium was measured as a function of [NaNO3] and the results

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Trivalent f-Element Intra-group Separation by Solvent Extraction 133

Fig. 3 Separation factors of some lanthanide for Dy Fig. 4 Dependency of lanthanides distribution on DTPA
as a function of sodium nitrate concentration concentration

Fig. 5 Dependency of lanthanides distribution on shaking Fig. 6 Dependency of lanthanides distribution on tempera-
time re tu

are summarized in Fig. 7. The DpH value increases is quite favorable for steady counter current operation.
with the increasing in [NO3-]. The increase was most
significant at initial pH=1.0, and DpH was always pos- 3. Basic Flow Sheet for Trivalent Actinide and
itive, i.e., proton was transferred to the organic phase Lanthanide Separation
through the back-extraction. DpH value was nearly zero In an actual process, the co-extraction of lanthanides
when the initial pH was about two. When the initial pH and trivalent actinides into a TRUEX solvent will be car-
was larger than 2.5, DpH was negative in most cases, i.e., ried out by treating a rather strong acidic nitrate medium

proton was transferred from organic phase. These find- like PUREX raffinate or concentrated waste solution. As
ings suggests a buffering effect of DTPA. This tendency the result, the loaded TRUEX solvent will inevitably

VOL. 35, NO. 2, FEBRUARY 1998

134
Fig. 7 Variation of pH (DpH) through back-extraction pro-
cedure
contain considerably high concentration of nitric acid,
for example, higher than 0.5M. Direct contact of such
a loaded solvent with the stripping solution results in
the increase of acidity. To achieve effective actinides(III)
and lanthanides(III) separation through stripping pro-
cess, the acidity must be kept low enough to make the
complexing with DTPA possible. Therefore, nitric acid
Fig. 8 Calculated distribution ratio
Y. KOMA et al.
should be stripped from the loaded solvent, keeping the
actinides and lanthanides in the solvent, before the se-
lective stripping with the DTPA solution.
In Fig. 8, the calculated distribution ratio of Am and
nitric acid are compared. The calculation was made by
the method of Chaiko(13). There is proper condition in
which the stripping of nitric acid is possible while re-
taining Am in the organic phase. With a solution of low
acidity and 0.3-0.5M NaNO3, the D value of Am which
is higher than 10 can be obtained and nitric acid is ex-
pected to be selectively stripped from the loaded solvent.
Introduction of this"acid stripping"will contribute to
pH stabilization in the subsequent process.
The basic flow sheet designed from the above discus-
sion is shown in Fig. 9. The scheme consists of four
steps. The organic solution is a general TRUEX solvent
and is not necessary to change its composition through-
out the sequential four steps. At the first step, trivalent
metals are extracted from acidic solution. The operating
condition of this step is same to that of typical TRUEX
process. The loaded TRUEX solvent will be contacted
with nitrate solution of pH 2 for reducing its acidity
below 0.01M in the second"acid stripping" step. The
concentration of nitrate anion in the stripping solution
should be prepared to 0.3-0.5M. A washing solvent is
provided to reduce the concentration of actinide in the
waste stream.
At the next step, Am and Cm will be back-extracted
with DTPA-nitrate solution. For the operation at room
temperature, the recommended composition of the strip-
ping solution is 0.05M DTPA and 2-4 M NaNO3, and pH
should be adjusted to about 2. In this actinides strip-
ping step, Am and Cm will be recovered into the aqueous
of Am and nitric acid from HNO3-NaNO3 solution
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
Trivalent f-Element Intra-group Separation by Solvent Extraction 135

Fig. 9 Conceptual flowsheet for trivalent acitinides and lanthanides separation

solution, while light lanthanide will be retained in the or- Table 1 Distribution ratio and separation factor of some
ganic phase. The behaviors of heavy lanthanide will not nuclides
be simple. Samarium and Eu will be distributed in both Organic solution: 0.2M CMPO-1.0M TBP in
n-dodecane (contacted with 0.1M HNO3-
phases. Most of Gd will be stripped together with triva- 1.0M NaNO3 solution containing radionu-
lent actinide. At the fourth lanthanides stripping step, clides)
the light lanthanide will be stripped with dilute nitric Aqueous solution: 0.05M DTPA-4M NaNO3
acid solution. The used solvent will be recycled to the solution (initial pH=2.0)
first extraction step.

4. Demonstration by Batchwise Extraction

As described so far, the TRUEX solvent and DTPA-
nitrate partition system would give the group separation
for light lanthanides and actinides. Before performing
the demonstration test of counter current operation, it
is worthwhile to ascertain the capability of the system by
Batchwise experiment using the loaded TRUEX solvent
which contains radioactive lanthanides and actinides.
Distribution ratio and separation factor of major nu- t Separation factor was calculated as a value to 241Am.
clides were obtained and are summarized in Table 1. For sample No. 2, the used solvent which had been
tt stored in
The pH value after back-extraction was estimated to be a hot cell for several months was used.

about 1.7 from the distribution ratio of 155Eu. As it

was quite difficult to adjust the acidity of the loaded sol-
vent, the pH value became smaller than the optimum
value. The complexing with DTPA did not proceed ef-
fectively in the present batchwise experiment, however,
it was found that the distribution ratio of Am and Cm is
smaller than Eu. Thus, it is expected that the separation
of Am and Cm from light lanthanides will be performed
by counter current operation. The separation factor for
Eu/Am and Am/Cm was about two. The difference is
too small to separate those elements.
IV. Conclusion
In the partition system of the normal TRUEX sol-
vent and a DTPA-nitrate solution, distribution behav-
iors of Ce, Nd, Eu and Dy were observed and effects of
acidity, [NO3-], [DTPA], temperature and shaking time
on their distribution ratios were clarified. Separation of
light lanthanides was mainly governed by complex for-
mation with DTPA. Based on these findings, a basic
flow sheet was proposed to separate trivalent actinides
and lanthanides. The flow sheet consists of four steps,
i.e., trivalent actinides and lanthanides extraction that is
identical to the original TRUEX process, acid stripping,
actinides stripping and lanthanides stripping. In batch-
wise experiment using radioactive nuclides, separation
factor of larger than 13 and 27 for Ce/Am and Cm/Eu,
respectively, were obtained. It is expected that Am and
Cm will be recovered together with Eu and heavier lan-
thanide, and will be separated from light lanthanides.

VOL. 35, NO. 2, FEBRUARY 1998

 Y. KOMA et al.
1 36

23[12 & 13], 1191 (1988).

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JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY